Microbial fuel cells - Applications for generation of electrical power and beyond.

A Microbial Fuel Cell is a bioelectrochemical device that exploits metabolic activities of living microorganisms for generation of electric current. The usefulness and unique and exclusive architecture of this device has received wide attention recently of engineers and researchers of various disciplines such as microbiologists, chemical engineers, biotechnologists, environment engineers and mechanical engineers, and the subject of MFCs has thereby progressed as a well-developed technology. Sustained innovations and continuous development efforts have established the usefulness of MFCs towards many specialized and value-added applications beyond electricity generation, such as wastewater treatment and implantable body devices. This review is an attempt to provide an update on this rapidly growing technology.

Slow magnetic relaxations in manganese(III) tetra(meta-fluorophenyl)porphyrin-tetracyanoethenide. Comparison with the relative single chain magnet ortho compound.

Mn(III) tetra(meta-fluorophenyl)porphyrin-tetracyanoethenide coordination polymer (abbreviated meta-F) was synthesized and crystallographically and magnetically characterized. The compound crystallizes in the space group C2/c with four equivalent molecules in the unit cell arranged along two symmetry related nonparallel linear chain directions. Magnetic properties were studied by SQUID dc magnetization and ac susceptibility techniques and high field-high frequency electron spin resonance (HF-ESR). Glassy transition to a ferromagnetic-like state is observed at 10 K accompanied by slow magnetic relaxations. The glassiness is interpreted as due to 3D domain wall pinning. In a bias dc magnetic field the width of the relaxation time distribution decreases and the relaxations become similar to the relaxations of the single chain magnet Mn(III) tetra(ortho-fluorophenyl)porphyrin-tetracyanoethenide (abbreviated ortho-F), for which comparative HF-ESR studies were also conducted in this work. Magnetic properties of these two compounds are compared, and the nature of magnetic relaxations in meta-F is discussed.

Temperature dependent current-voltage characteristics of iron-phthalocyanine thin films.

The current-voltage (I-V) characteristics of the crystalline alpha-phase iron phthalocyanine (FePc) thin films grown by molecular beam epitaxy have been investigated by using a planar geometry in which the metal electrodes are separated by 15 microm. By carrying out the room temperature I-V measurements on vacuum annealed (200 degrees C for 30 min under 10(-6) torr) FePc thin films under vacuum and after exposing them to the air, we demonstrate that the hysteresis in FePc films is intimately related to the filling and de-filling of surface traps created by chemisorbed oxygen. The presence of chemisorbed oxygen has been confirmed by the X-ray photoelectron spectroscopy. Room temperature I-V characteristics of air exposed films showed ohmic conduction in the lower voltage range and space-charge-limited-conductivity (SCLC) in the relatively high voltage. Temperature dependent measurements show that the hysteresis disappears at 250 K and the surface traps are distributed in energy about 0.22 eV deep.

Electrical characterization of self-assembled monolayers of alkyltrichlorosilanes on native oxide of silicon.

The octadecyltrichlorosilane (C18), dodecyltrichlorosilane (C12) and octyltrichlorosilane (C8) monolayers have been deposited on the native oxide of silicon by self-assembly technique. The morphology of the monolayers studied by atomic force microscopy revealed an average roughness of approximately 1.0 A. The Fourier Transform Infra Red Spectroscopic measurements revealed the presence of peaks at approximately 2848 and 2915 cm(-1) indicating the formation of densely packed monolayers. The current density versus voltage (J-V) measurements using mercury drop as counter electrode showed tunneling current between 10(-5) to 10(-8) A/cm2 at 1 V indicating the excellent dielectric behaviour of these monolayers. The J-V data were fitted to Simmons theory of tunneling which yielded an effective electron energy barrier height of 1.6 +/- 0.2 eV and the effective mass of electron tunneling through the barrier was found to be 0.3 +/- 0.03 m(e). The tunneling decay factor beta was estimated from the current density values measured as a function of thickness of the monolayer and was found to be 0.28 +/- 0.02 A(-1).

Application of aligned ZnO nanowires/nanobelts as a room temperature NO gas sensor.

Gas sensing properties of devices fabricated using ZnO nanowires/nanobelts (NS) aligned between two electrodes using dielectrophoresis technique were investigated. ZnO nanostructures were synthesized by carbothermal method. The devices were characterized as gas sensors and showed high sensitivity for detection of NO gas at room temperature. Typical sensor response, defined as the relative change in resistance, due to the introduction of the gas was found to be approximately 500% for 40 ppm of NO gas. The devices showed average response and recovery times of about 30 s and 1 min respectively. The results demonstrate the potential of fabricating nanosized sensors using single nanowires/nanobelts.

Time response and stability of porous silicon capacitive immunosensors.

The time response of affinity sensors made with nanostructured materials is a topic of considerable interest, since affinity sensors made with nanostructured materials provide greater sensitivities than corresponding planar crystalline devices but at the cost of stability and drift. We present a study of the time response of capacitive immunosensors made using porous silicon and ultrathin room temperature anodic oxide. It was found that sensor drift can be substantial but can be reduced by subjecting the capacitive immunosensor in buffer to an anodic bias that is larger than the bias at which sensor capacitance is measured. By measuring sensor response before the addition of the analyte and using it for baseline correction after addition of the analyte, the effect of nonspecific sensor drift can be further reduced. We observed that after the addition of the analyte to the porous silicon immunocapacitor, there is a fast decrease in capacitance (order of tens of seconds) followed by a slow increase (order of tens of minutes), which models well as a sum of exponents with a fast exponential decay followed by a slow exponential rise. Possible processes that can give rise to such a response are perturbations of the double layer for the fast decay and column resistance switching for the slow rise.

Growth of highly oriented crystalline polyaniline films by self-organization.

Silicon substrates with (100) orientation were modified with amino-silane self-assembled monolayer (SAM) to provide amino (NH(2)) moieties at the substrate surface. Self-organization of polyaniline during chemical polymerization, on this modified surface, leads to the growth of highly oriented films at the substrate-polymer interface. The morphology studied using scanning electron microscopy and atomic force microscopy revealed the formation of polymer film with well faceted pyramidal crystallites. XPS and FTIR spectroscopy were used to analyze the chemical structure of the film. X-ray diffraction measurements show the crystalline nature of the polyaniline, whose lattice parameters are in agreement with the reported values. This study underlines the importance of a SAM in deciding the structure and morphology of the deposited polymer.

Electrostatic ion trap and Fourier transform measurements for high-resolution mass spectrometry.

We report on the development of an electrostatic ion trap for high-resolution mass spectrometry. The trap works on purely electrostatic fields and hence trapping and storing of ions is not mass restrictive, unlike other techniques based on Penning, Paul, or radio frequency quadrupole ion traps. It allows simultaneous trapping and studying of multiple mass species over a large mass range. Mass spectra were recorded in "dispersive" and "self-bunching" modes of ions. Storage lifetimes of about 100 ms and mass resolving power of about 20,000 could be achieved from the fifth harmonic Fourier transform spectrum of Xe ions recorded in the self-bunching mode.

Polymer-surfactant layered heterostructures by electropolymerization of phenosafranine in Langmuir-Blodgett films.

Langmuir-Blodgett (LB) films of the water-soluble dye phenosafranine (PS) have been prepared by its adsorption from aqueous dye solution to an arachidic acid (AA) monolayer at the air-water interface. Atomic force microscopy (AFM) images of the LB films revealed the effect of change in pH of deposition on the degree of complexation of AA with the PS dye. Well-defined circular islands and holes were observed which disappeared with the increase in pH. Polarized absorption studies indicated that the dye molecules are oriented uniaxially with their long axis titled at a constant angle to the surface normal of the LB film. Within the restricted geometry of the LB film, the PS dye was electropolymerized to form a two-dimensional film of poly(phenosafranine) sandwiched between arachidic acid layers. The film was characterized by IR spectroscopy, cyclic voltammetry, and AFM. X-ray diffraction studies reveal the presence of a layer structure in the AA-PS LB film before and after polymerization. The polymer film showed highly anisotropic electrical conductivity of ca. 10 orders of magnitude. This indicates the formation of two-dimensional polyPS layers between arachidic acid layers resulting in a layered heterostructure film having alternate conducting and insulating regions. Also, the conductivity of the polyPS prepared from LB film was found to be approximately 2.5 times higher than the conductivity of polyPS prepared by solution polymerization method.

Sodium chloride and ethanol induced sphere to rod transition of triblock copolymer micelles.

Dynamic light scattering (DLS), small-angle neutron scattering (SANS), and viscosity studies have been carried out to examine the influence of NaCl and ethanol on the structure of triblock copolymer [(EO)20(PO)70(EO)20] (EO = ethylene oxide; PO = propylene oxide) micelles in aqueous medium. The studies show that while the pure triblock copolymer solutions do not show any significant growth of the micelles on approaching the cloud point, the presence of a small amount of ethanol (5-10%) induces a sphere to rod shape transition of micelles at high temperatures. Interestingly, this ethanol induced sphere to rod transition of micelles can be brought down to room temperature (25 degrees C) with the addition of NaCl. It is also found that NaCl alone cannot induce such sphere to rod transitions and excess ethanol suppresses them by increasing their transition temperature.

A Three-Dimensional Ferrimagnet with a High Magnetic Transition Temperature (TC ) of 53 K Based on a Chiral Molecule.

The transparent, double bridged-(R)-spiral three-dimensional polymeric complex K0.4 [Cr(CN)6 ][Mn(S)-pn](S)-pnH0.6 ((S)-pn=(S)-1,2-diaminopropane) has been synthesized and characterized (see X-ray structure; Cr: brown, Mn: red, C: gray, N: blue, K: green). Magnetic measurements on the complex show that the MnII and CrIII ions interact ferrimagnetically and magnetic transition occurs at 53 K (Curie temperature).

Spin interactions in mineral libethenite series: evolution of low-dimensional magnetism.

Interesting magnetic properties and spin-exchange interactions along various possible pathways in the half-integral spin quantum magnetic tetramer system: A(2)PO(4)OH (A=Co, Cu) are investigated. Interplay of structural distortion and the magnetic properties with the evolution of localized band structure explain the gradual transition from a three-dimensional antiferromagnet to a low-dimensional frustrated magnetic system along the series. A detailed study of the exchange mechanism in this system explores various possibilities of complex magnetic interaction. The electronic structure of this series, studied with the help of different appropriate density functional approaches such as Nth order muffin-tin orbital (NMTO) and plane-wave pseudopotential calculations incorporating onsite Coulomb repulsion (U), identifies the underlying magnetic exchange mechanism of this series. Thereafter a generalized minimal model spin-Hamiltonian is constructed for the low-dimensional system. Solution of this model Hamiltonian within first-order perturbation theory results in the evaluation of spin-gap in the spin-tetramer system. In addition, the effects of size confinement and volume reduction on the relevant exchange integrals and spin-gap of the low-dimensional system are also discussed.

Charge transport in ultrathin iron-phthalocyanine thin films under high electric fields.

The temperature dependent current-voltage (J-V) characteristics of 20 nm thick iron-phthalocyanine films are investigated in the temperature range of 300-30 K, and in the bias range of ±200 V. In the temperature range of 300-100 K, the charge transport is governed by bulk-limited processes with a bias dependent crossover from Ohmic (J∼V) to exponentially distributed shallow trap mediated space-charge-limited conduction (J∼V(α), α ≥ 2) to space-charge-limited conduction with field enhanced mobility (lnµâˆ¼E(1/2)). However, at temperatures less than 100 K, the charge transport is electrode-limited, and undergoes a bias dependent transition from Schottky (lnJ∼V(1/2)) to multistep tunneling. From shallow trap mediated space-charge-limited conduction data the estimated room temperature mobility was found to be ∼1.9 cm(2) V (-1) s(-1). The high mobility of films is attributed to better structural organization due to the face-on stacking of molecules, which is supported by x-ray diffraction and UV-visible spectroscopy data.

Room temperature ppb level Cl2 sensing using sulphonated copper phthalocyanine films.

We present room temperature chemiresistive gas sensing characteristics of drop casted sulphonated copper phthalocyanine (CuTsPc) films. It has been demonstrated that these films are highly selective to Cl(2) and the sensitivity in the 5-2000 ppb range varies linearly between 65 and 625%. However, for concentrations >or=2000 ppb, the response becomes irreversible, which is found to be due to the chemical bond formation between Cl(2) and SO(3)Na group of CuTsPc films. The X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) data confirms the oxidation of SO(3)Na group by Cl(2) gas.

Effectiveness of two different HDR brachytherapy regimens with the same BED value in cervical cancer.

PURPOSE: To analyze the effectiveness of biologically effective dose (BED) in two different regimens of HDR brachytherapy keeping the same total BED to point A and to compare the relationship of overall treatment time in terms of local control and bladder and rectal complications. MATERIAL AND METHODS: The study included two groups comprising a total of 90 cervical cancer patients who underwent external beam radiotherapy (EBRT) followed by HDR intracavitary brachytherapy (ICBT). EBRT treatment was delivered by a Co-60 teletherapy unit to a prescribed dose of 45 Gy with 1.8 Gy per fraction in 25 fractions over a period of five weeks. Parallel opposed anterior-posterior (AP/PA) fields with no central shielding were used, followed by the HDR ICBT dose, to point A, of either two fractions of 9.5 Gy with a gap of 10 days, or three fractions of 7.5 Gy with a gap of 7 days between the fractions. Gemcitabine (dose of 150 mg/m2) was given weekly to all the patients as a radiosensitizer. The calculate BED3 to point A was almost the same in both groups to keep the same late complication rates. The doses, and BED10 and BED3, were calculated at different bladder and rectal point as well as at the lymphatic trapezoid points. During and after treatment patients were evaluated for local control and complications for 24 months. RESULTS AND CONCLUSIONS: Doses and BEDs at different bladder, rectal and lymphatic trapezoid points, local control, and complications in both HDR ICBT groups did not have statistically significant differences (p > 0.05). Both HDR ICBT schedules are well tolerable and equally effective.

Chlorine gas sensors using one-dimensional tellurium nanostructures.

Tellurium nanotubes have been grown by physical vapor deposition under inert environment at atmospheric pressure as well as under vacuum conditions. Different techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and optical absorption have been utilized for characterization of grown structures. Films prepared using both types of tellurium nanotubes were characterized for sensitivity to oxidizing and reducing gases and it was found that the relative response to gases depends on the microstructure. Nanotubes prepared at atmospheric pressure (of argon) showed high sensitivity and better selectivity to chlorine gas. Impedance spectroscopy studies showed that the response to chlorine is mainly contributed by grain boundaries and is therefore enhanced for nanotubes prepared under argon atmosphere.

Microscopic understanding of negative magnetization in Cu, Mn, and Fe based Prussian blue analogues.

A crossover of the field-cooled magnetization from positive to negative has been observed below the magnetic ordering temperature (17.9 K) in a multimetal Prussian Blue analogue (PBA), Cu_{0.73}Mn_{0.77}[Fe(CN)_{6}].zH_{2}O. The reverse Monte Carlo (RMC) modeling (using the program RMCPOW) has been used to derive the various scattering contributions (e.g., nuclear diffuse, nuclear Bragg, magnetic diffuse, and magnetic Bragg) from the observed neutron diffraction patterns. The RMC analysis combined with the Rietveld refinement technique show an antiferromagnetic ordering of Mn moments with respect to the Cu as well as the Fe moments. Our study gives the first neutron magnetic structure evidence towards the microscopic understanding of the negative magnetization in the PBAs. This information can be effectively utilized to design suitable PBAs for making multifunctional devices.

Improved performance of polyaniline-uricase biosensor.

Uricase has been covalently immobilized using glutaraldehyde as cross-linker onto electrochemically synthesized polyaniline (PANI) films. These PANI-uricase electrodes have been characterized using spectroscopic, cyclic voltammetry and impedance measurements. The morphology and covalent linkage of uricase lead to high enzyme loading and better shelf life. The value of the Michaelis-Menton constant obtained as 5.1x10(-3) mM L(-1) for the immobilized uricase compared to 3.4x10(-1) mM L(-1) for the free uricase enzyme, suggests enhancement in affinity and/or activity of uricase attached to PANI. The influence of pH, temperature and concentration on electrode activity were studied. The enzyme electrodes were found to retain 95% of activity after 17-18 weeks when stored at 4 degrees C. These electrodes have a response time of about 60 s and have been used to measure uric acid concentration in serum. These PANI-uricase electrodes can be used for about 30 times for electrochemical measurements while retaining about 90% of its activity indicating improved performance.

Self assembled monolayers on silicon for molecular electronics.

We present an overview of various aspects of the self-assembly of organic monolayers on silicon substrates for molecular electronics applications. Different chemical strategies employed for grafting the self-assembled monolayers (SAMs) of alkanes having different chain lengths on native oxide of Si or on bare Si have been reviewed. The utility of different characterization techniques in determination of the thickness, molecular ordering and orientation, surface coverage, growth kinetics and chemical composition of the SAMs has been discussed by choosing appropriate examples. The metal counterelectrodes are an integral part of SAMs for measuring their electrical properties as well as using them for molecular electronic devices. A brief discussion on the variety of options available for the deposition of metal counterelectrodes, that is, soft metal contacts, vapor deposition and soft lithography, has been presented. Various theoretical models, namely, tunneling (direct and Fowler-Nordheim), thermionic emission, Poole-Frenkel emission and hopping conduction, used for explaining the electronic transport in dielectric SAMs have been outlined and, some experimental data on alkane SAMs have been analyzed using these models. It has been found that short alkyl chains show excellent agreement with tunneling models; while more experimental data on long alkyl chains are required to understand their transport mechanism(s). Finally, the concepts and realization of various molecular electronic components, that is, diodes, resonant tunnel diodes, memories and transistors, based on appropriate architecture of SAMs comprising of alkyl chains (sigma- molecule) and conjugated molecules (pi-molecule) have been presented.

Polyaniline nanoparticles prepared in rodlike micelles.

The effect of aniline hydrochloride (AHC) on the size and shape of sodium dodecyl sulfate (SDS) micelles has been investigated by dynamic light scattering. A monotonic decrease in the diffusion coefficient of the micelles was observed with an increase in AHC at fixed SDS concentration. This was ascribed to prolate ellipsoidal growth of the micelles due to decrease of the effective headgroup area/molecule by adsorption of AHC on SDS micelles. The length of the micelles can be tuned by controlling the ratio of concentrations of AHC to SDS. Polymerization of aniline in micelles of different sizes leads to the formation of colloidal polyaniline with variable sizes. A direct correlation between size ofmicelles and size ofpolyaniline particles was observed. Combination of static and dynamic light scattering experiments reveal that the conformations of the polymer do not change significantly with size of the colloid.